Polyhalocycloalkenyl derivatives of abietic acid



Patented Feb. 2, 1965 3,163,556 PELYI EALUQYQLQALKENYL DEREVATEVEE) i @h AEEETEQ ACE) John l. Luvisi, Fart; Ridge, iii, assignor to Universal! Produets-Qoinpany, Des Plaines, iih, a corporation of Deiaware r No Drawing. Fiied No .8, 1961, Ser. No. lfiiifii ti This application is a continuation-in-part of my copending application Serial Number 763,448, filed September 26, 1958, noW abandoned,

This invention relates to a process for preparing halo substituted polycyclic compounds and more particularly to a process for preparing halo substituted cyclic derivatives of polycyclic organic acids.

A further embodiment of this, invention resides in a hexahalobicycloheptenyi derivative of abietic acid A specific embodiment of this invention. is found in a hexachlorobicycloheptenyl derivative of abietic acid.

Gther objects and embodiments will be found in the following detailed description ofthis invention. Halo substituted allcadiene or halo substituted cycloalkadiene derivatives of abietic'acid will find particular United States Patent Ofifice ose in the chemical field as insecticides as well as iungi- ,cides, aigaecides, and herbicides. For example, the condensation product which results from the reaction he tween abietic acid and,hexachlorocyclopentadiene will be. used eiiectively as an insecticide, especially against houseflies. in additiomthe reaction products of this invention may also find uses as intermediatesin the preparation of resins, pharmaceuticals, plastics, etc. For purposes of this invention the term halo substituted alkadiene" and fhalo substituted cycloalkadiene will refer to bothrnono and polyhalo compounds. Furthermore, the term polyhalocycloalkenyl as used hereinafter in the specification and appended claims Will refer to both monocycloand bicycloY-compounds. l As hereinbetore set forth the present invention relates to a process for preparing halo substituted polycyclic compounds by reacting a halo substituted allradiene or halo substituted cycloallcadiene 'With abietic acid. The abietic acid which is used in the process of this invention in equilibrium with levopirnaric acid. Thereforaan example of the process of this invention could be illustrated by the following equation in which abietic acid is condensed with hexachlorocyclopentadiene to iorm'the isomeric heaachlorobicycio- [2.2 l -2-hepteny1 derivatives of abietic acid.

Abietic acid 1,4-dichloro-2-dich1oromethyl-1,3-butadilei1e, t t

CH COOH Devopimaric acid isomeric mixture Unsaturated compounds containing a halogen substituent which may be reacted with the abietic acid-levopirnaric acid equilibrium mixture in the process of the present invention include straight-chain diolefins having the general formula: i

X X V V Xvo=h o=ox=Y v in which X is independently selected from the group consisting of hydrogen, aikyl, haloalkyl or halogen. radicals having an atomic weight of from 35 to 127, (i.e., chlorine, bromine or iodine), at least one X being halogen or haioalkyl and Y is independentlyselected from the group consisting of alizyi, haloallryl, and hydrogen radicals; or

poiyhalocycloalkadienes having the general formula; 40 I i (XGX)n I:

i 1 X t in vvhich X has the sat 1e meaning as above and n is 1 or 2. Examples of these compounds include haloalkadienes such as i i landZ-chloro-Lihutadiene,

1,3 01: 2,3-and 1,4-dich1oro-i,3-butadiene, I land 2-brorno l,3-butadiene, l,3-, 2,3- and 1,4-dibromo-L3-butadiene, 1,3-, 2,3- and l,4 diiodo-L3-butadiene,, 1,2,3trichloro-1,STbutadiene,

V '1,2,3-tribromo-1,3-butadiene,

1 and 2-iodo-l,3-butadiene,

, 1,Z-diiodo-Lit-butadiene,

l,2,4stribromo 1,3-butadiene,

1,2,4-triiodo-1,3-butadiene, l,2,3,4--tetrachloro-LES-britadiene, l,2,3,4-tetrabrorno-1,3-butadiene, 1,2,3,4-tetraiodo-l,3-butadiene, 1,3-dichloro-2-methyl-1,3Ebutadiene, 1,4-dichloro-V2-methyl-1,3}butadiene, l,3,4-trichloro-2 methyl-1,3-butadiene, l,4-dichloro-2-chloromethyl-1,3-bi1tadiene,

1,3-dibrorno-2'methy1 l,3-butadiene,

' availability and lower cost.

ease,

and halocycloalkadienes such as halogenated 1,3-cyclopentadienes which forpurposes of this invention will be designated as halogenated cyclopentadienes including 1- chlorocyelopentadiene, 1,2- and other dichlorocyclopentadienes, 1,2,3- and other trichlorocyclopentadienes, 1,2,3,4- and other tetrachlorocyclopentadienes, l,2,3,4,5- and other pentachlorocyclopentadienes, hexachlorocyclopentadiene,the corresponding bromoand iodo-derivatives, etc. It is also contemplated within the scope of this invention. that polyhalo substituted conjugated cyclohexadienes such as l,Z-dichloro-1,3-cyclohexadiene, 1,2,3'-trichloro-l,3- cyclohexadiene, octachloro-l,3-cyclohexadiene, etc., 1,2- .dibromo 1,3 cyclohexadiene, 1,2,3 trioromo l,3- cyclohexadiene, octabromo-1,3-cyclohexadiene, iodo-1,3-cyclohexadiene, 1,2,3-triiodo-1,3-cyclohexadiene, octaiodo-1,3-cyclohexadiene, etc., may also be used. Furthermore, it is contemplated within the scope of this invention that fluorine analogs of the aforementioned unsaturated compounds such as hexafiuorocyclopentadiene or 2,3-dii'luoro-l,3-butadiene may also be used, although not necessarily with equivalent results. Generally speaking the iodine, bromine and chlorine containing com- 'poundsare preferred because of their relatively greater templated that polyhaloalkadienes and polyhalocycloalkadienes which are used in this process may contain more than one species of halo substituents, such as, for example,

1,2-dichloro-3-bromo-1,3-butadiene, 1-chloro-3bromo-1,3-butadicne, 1iodo-3-chloro-1,3-butadiene, 2-bromo-3-chloro-1,3-butadiene, 1,4-dichloro-2-bromomethyl-1,3-butadiene, 1,4-dlChIOIOZriOdOHIGthYI-J ,3-butadiene, l-chloro-Z-bromocyclbpentadiene, 1,2-dichloro-3-bromocyclopentadiene, 1,2-dichloro-5,S-dibromocyclopentadiene, etc.,

although not necessarily with equivalent results.

Generally speaking the process of this invention will be effected at elevated temperatures in the range of from about 100 to about 200 C. or more.

90 C.; when toluene is used the reaction will be elfected at a temperature of from about 100 to about 120 (3.,

In addition, it is also con In the preferred embodiment of the invention the reaction is effected in or when m-xylene is .used the reaction is effected at a 1 temperature in the range of from about 1305 to about 150 C. etc.

lants and also plant growth, regulators, the particular compounds having many of the features desired of ma to room temperature.

terials for this purpose. They are, for example, toxic to insects which are destructive of plant life and materials normally subject to insect infestation, their toxic effects being manifested by contact of the poison with the insect. The insecticides comprising the present compounds are thus effective against chewing as well as sucking types of insects. that when applied to plant life intended for subsequent human consumption, the plants when harvested and after allowing a reasonable time for evaporation-of the applied insecticide therefronr-retain none of the toxicant to prevent use of the plant for consumption as food. On the other hand, the compounds are of sufficiently limited volatility to be retained on the insect for the time required to accomplish the toxic effects of the compounds. T 1e volatility and retentive capacity of the compounds maybe varied at will by combining them with suitable fixing agents which reduce or promote their volatilization, as desired. Thus, the compounds may be dissolved in a suitable high boiling solvent, such as a mineral or vegetable oil, petroleum, etc; a wax, such as paramn, beeswax, etc; a high molecular Weight alcohol or ether such as myricyl alcohol, dibutyl ether, etc.; or they may ponent'may be preferred in some instances where deep.

penetration of the insecticide is desired, as in the treatment of fibrous material, for example, Wood termites. For other purposes, the required concentration of active components in the formulation may be asv low as 0.1%, as for example in the treatment of fabrics for destroying moth larvae. In utilizing the present insecticidal compounds against most insects, a composition con 7 taining from about 0.l% to-about 5% by Weight of the active component is highly effective. The choice of the most desirable solvent or dispersant further depends upon the method utilized to applythe insecticidal composition to the infested article. For example, a low molecular Weight, normally gaseous carrying agent for the active insecticidal component, such. as propane, butane, the

Freons, etc., may be compressed and liquefied into a small bomb containing the insecticide. Upon release of pressure from the bomb, the liquefied carrier vaporizes and suspends a quantity of the active component therein, thus providing a convenient spraying method of applying the insecticide. solved in a liquid carrier, such as kerosene, an alcohol, ester, etc., and the resulting solution atomized by a suitable spraying device.

The process of this invention may be effected in any suitable manner and may comprise either a batch or a- For example, when a batch continuous type operation. type operation is used a quantity of'the starting materials comprising the abietic acid and the halo substituted alkadiene or cycloalkadiene is placed in an appropriate condensation apparatus provided with heating and stirring means and a reflux condenser. The selected organic diluent is also placed in the condensation apparatus which is thereafter sealed and heatedto approximately the reflux temperature of the diluent. The apparatus and contents thereof are maintained atthis temperature for a predetermined residence time, at the'end of which time the apparatus and contents thereof are allowed to cool The desired condensation product is separated from unreacted materials,-purified and recovered by conventional means such as fractional distillation, crystallization, etc.

The compounds are sufficiently volatile so The particular formu The active component may also be disfected in a continuous type operation.

hydrated bauxite, alumina and the like.

areasee The process of the present invention may also be ef- In this type of operation the starting materials are continuously charged to a reactor which is maintained at the desired operating conditions of temperature and pressure. If so desired the reactants may be charged through separate lines or may be admixed prior to entry into said reactor and charged thereto in a single stream. The reactor may comprise an unpacked vessel or coil or may be lined with an absorbent packing material such as fire brick, de-

In addition the inorganic diluent is also charged to said reactor through separate lines or said diluent may be admixed with one or both of the starting materials before entry into said reactor and charged thereto in a single stream. After a predetermined residence time has been completed the condensation product is continuously withdrawn, sep arated from the reactor efiluent, purified and recovered by the conventional means hereinbefore set forth, while the unreacted starting materials may be separated and recycled to form a portion of the feed stock.

The following examples are given to illustrate the process of the present invention, which, however, are not intended to limit the generally broad scope of the present invention in strict accordance therewith.

Example I A solution of 30.2 g. (0.1 mole) of abietic acid and 27.3 g. (0.1 mole) of hexachlorocyclopentadiene in about 51 g. of toluene was heated under reflux at a temperature of about 121 C. for about 3 hours after which time the toluene was gradually distilled off thus permitting the temperature of the solution to rise. After approm' mately 45 g. of toluene was removed during a period of aboutl4 hours the temperature rose to about 170 C. The solution was then heated for an additional period of minutes without any further. removal of toluene, after which the product was allowed to cool, then taken up in pentane, washed with water, dried and subjected to fractional distillation at reduced pressure. Only 3 of unreacted hexachlorocyclopentadiene' was removed. Fifty grams of the desired adduct, comprising the isomeric hexachlorobicycloheptenyl derivatives of abietic acid was separated and recovered as a viscous oil.

Example I] -water, dried and subjected to fractional distillation, the

desired adduct comprising the isomeric hexabromobicycloheptenyl derivatives of abietic acid being recovered therefrom.

Example III A solution of 12.3 g. (0.1 mole) of 1,4-dichloro-1,3- butadiene and 30.2-g. (0.1 mole) of abietic acid in 50 g. of o-xylene is heated under reflux conditions for a period of about 6 hours, after which the product is recovered in a manner similar to that set forth in Examples 1 and II above. The condensation product comprising the isomeric dichlorocylohexenyl derivative of abietic acid. is separated and recovered.

Example IV A solution of 21.2 g, 0.1 mole) of l,4-dibromo-1,3'

butadiene and 30.2 g. (0.1 mole) of abietic acid in 50; g. of toluene is treated in a manner similar to that set; forth in the above examples. The desired adduct com.- prising the isomeric dibromocyclohexenyl derivative. of.' abietic acid is separated and recovered.

Example V An insecticidal composition isprepared by dissolving 1 g. of the isomeric hexachlorobicycloheptenyl derivative; of abietic acid in 2 cc. of benzene and adding cc;. of water using Triton X-100 as an emulsifying agent. The resulting solution is sprayed into a cage containing;

common houseflies and causes a 100% knock-down and.

eventual kill.

Similartests of other insecticides of ExamplesII, 1111 and TV show that these compounds, like those of Example: I will exhibit an effective knock-down ability with es-- cyclopentadiene, polychlorocyclohexadiene and polybrornocyclohexadiene. 2. A hexachlorobicycloheptenyl derivative of abietic acid resulting from the condensation of abietic acid with hexachlorocyclopentadiene at a temperature in the range V i of from about 100 to about 200 C.

3; A hexabrornobicycloheptenyl derivative of abietic acid resulting from the condensation of abietic acid with 'hexabromocyclopentadiene at a temperature in the range of from about 100 to about 200 C.

4. A dichlorocyclohexenyl derivative of abietic acid resulting from the condensation of abietic acid with 1,4- dichloro-1,3-butadiene at a temperature in the range of from about 100 to about 200 C.

5. A dibromocyclohexenyl derivative of abietic acid resulting from the condensation of abietic acid with 1,4-.

dibromo-l,3-butadiene at a temperature in the range of from about 100 to about 200 C.

References Cited in the file of this patent UNITED STATES PATENTS Peters May 27, 1952 Herzfeld et al. Aug. 12, 1952 OTHER REFERENCES a (1956), page 4883. 

1. A POLYHALOCYCLOALKENYL DERIVATIVE OF ABIETIC ACID RESULTING FROM THE CONDENSATION OF ABIETIC ACID AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 200*C. WITH A HALOGEN-CONTAINING UNSATURATED HYDROCARBON SELECTED FROM THE GROUP CONSISTING OF POLYCHLORO-BUTADIENE, POLYBROMO-BUTADIENE, POLYCHLORO-ALKYLBUTADIENE, POLYBROMOALKYLBUTADIENE, POLYCHLOROCYCLOPENTADIENE, POLYBROMOCYCLOPENTADIENE, POLYCHLOROCYCLOHEXADIENE AND POLYBROMOCYCLOHEXADIENE. 